WO2008003273A2 - Substrat anticorrosion et son procédé de production - Google Patents

Substrat anticorrosion et son procédé de production Download PDF

Info

Publication number
WO2008003273A2
WO2008003273A2 PCT/DE2007/000913 DE2007000913W WO2008003273A2 WO 2008003273 A2 WO2008003273 A2 WO 2008003273A2 DE 2007000913 W DE2007000913 W DE 2007000913W WO 2008003273 A2 WO2008003273 A2 WO 2008003273A2
Authority
WO
WIPO (PCT)
Prior art keywords
layer
substrate
phosphating
organically modified
modified polysiloxane
Prior art date
Application number
PCT/DE2007/000913
Other languages
German (de)
English (en)
Other versions
WO2008003273A3 (fr
Inventor
Gunter Heiche
Peter König
Original Assignee
Gerhard Heiche Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Gerhard Heiche Gmbh filed Critical Gerhard Heiche Gmbh
Priority to EP07764332A priority Critical patent/EP2041333A2/fr
Publication of WO2008003273A2 publication Critical patent/WO2008003273A2/fr
Publication of WO2008003273A3 publication Critical patent/WO2008003273A3/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C23C22/74—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process for obtaining burned-in conversion coatings
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2201/00—Polymeric substrate or laminate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2350/00—Pretreatment of the substrate
    • B05D2350/10—Phosphatation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

Definitions

  • the invention relates to a corrosion-resistant substrate, in particular a substrate or a part having a Cr (VI) -free corrosion-resistant coating and a method for the production thereof.
  • Steel and aluminum metal sheets and pieces are often provided with a coating that protects the sheet or part against attack by corrosive media.
  • This coating can also improve the adhesion of coatings applied thereto, further improving the corrosion resistance of the part.
  • the corrosion protection that provides the coating is tested according to specified test conditions, for example via salt spray tests, as per DIN 50 021 SS or outdoor weathering.
  • the coated blank metal is also sufficiently corrosion resistant without additional painting, gluing or rubber coating. This is desirable for parts, such as screws, which are to be installed in a larger system and to fit exactly to a second part.
  • the object of the invention is therefore to specify a Cr (VI) -free corrosion-resistant substrate which has better corrosion resistance in highly corrosive atmospheres, in particular in acidic atmospheres, and a process for the production thereof.
  • a corrosion-resistant substrate is specified with a Cr (VI) -free, corrosion-resistant, three-layer coating.
  • the substrate consists essentially of a phosphatizable steel or of a phosphatable Fe-based alloy.
  • a first phosphating layer is disposed directly on the base material of the substrate.
  • the second layer of the three-layer corrosion-resistant coating is a silane layer which is disposed directly on the phosphating layer.
  • the top third layer is an organically modified polysiloxane layer disposed directly on the silane layer.
  • the corrosion-resistant coating according to the invention thus consists of three layers which are each free of Cr (VI).
  • the base material of the substrate consists essentially of a phosphatizable steel or a phosphatable Fe-based alloy. This part thus serves as the basic substrate for the three-layer coating. The coated part thus provides the corrosion resistant substrate.
  • the second silane layer is disposed directly between the first phosphating layer and the third polysiloxane layer and serves as an additional adhesion promoter.
  • the combination of the three layers of the inventive coating on the phosphatizable steel or Fe-based Fe alloy substrate provides better corrosion resistance.
  • the three-layer coating provides the possibility of separately optimizing the properties of the three layers in order to achieve better corrosion resistance.
  • the adhesion of the silane layer to the phosphated surface of the base substrate can be optimized so that the entire three-ply coating does not detach from the base substrate and the surface of the substrate is completely covered.
  • the third organically modified polysiloxane layer can be optimized so that it adheres well to the silane layer and covers the silane layer well.
  • the third layer in principle, need not have good adhesion with the substrate material or with the phosphating layer.
  • the surface of the third organically modified polysiloxane layer can be optimized to have properties not exhibited by the lower two layers.
  • the third outer polysiloxane layer may, for example, have a self-cleaning effect due to a nanoscale surface microstructure, the so-called lotus effect.
  • the phosphating layer may be a wet-chemically applied layer and may be zinc phosphating, zinc-calcium phosphating, zinc-manganese phosphating, manganese phosphating or chlorate-accelerated zinc phosphating.
  • the phosphating layer may thus comprise zinc or zinc and nickel or an alkali metal or zinc and calcium or manganese.
  • the phosphating layer may have a known composition and may be applied directly to the steel or the Fe alloy by known
  • the silane layer is deposited from solution, the solution being free of Cr (VI) salt.
  • the silane layer has a thickness d 2 , where 0, l ⁇ m ⁇ d 2 ⁇ 5 microns.
  • the second wet-chemically applied silane layer may comprise aminopropyltriethoxysilane.
  • the organically modified polysiloxane layer has a thickness di, where l ⁇ m ⁇ di ⁇ 30 ⁇ m, preferably 2 ⁇ m ⁇ di ⁇ 25 ⁇ m, 5 ⁇ m ⁇ d x ⁇ 25 ⁇ m or 5 ⁇ m ⁇ di ⁇ 15 ⁇ m.
  • a thinner layer has the advantage that the layer can be applied more quickly, so that the production costs are reduced. Furthermore, the material costs are reduced.
  • a thicker layer may be advantageous to improve the coverage of the layer on the substrate. A thicker layer may provide improved corrosion resistance and thus extend the life of the substrate.
  • the organically modified polysiloxane layer has a cured crosslinked polymer network. The polysiloxane layer according to this embodiment can thus be referred to as a lacquer.
  • the organomodified polysiloxane layer comprises epoxysubstituted polysiloxanes which are crosslinked via inherently blocked isocyanates to form a polymer network.
  • epoxysubstituted polysiloxanes which are crosslinked via inherently blocked isocyanates to form a polymer network.
  • the organically modified polysiloxane layer comprises reaction products of glycidyloxypropyltrimethoxysilane and blocked isocyanates.
  • the third topmost polysiloxane layer is made to be dense and homogeneous and to have a self-cleaning effect due to low surface tensions.
  • the contact angle may be, for example, 110 °.
  • This high density and homogeneity is realized by a sol-gel formation mechanism in which the layer is formed.
  • the deposition conditions as well as the curing conditions may be selected to form the second top polysiloxane layer over nanoscale components to produce a dense homogeneous layer.
  • the cured crosslinked polysiloxane layer may be nanocrystalline.
  • the organically modified fected polysiloxane layer composed of nanoscale particles.
  • the base substrate consists of a steel whose alloying additives Me contribute at most 5 percent by weight, where 0 ⁇ Me ⁇ 5 percent by weight, remainder Fe, whereby carbon is not included.
  • the maximum limiting concentration is at most 4% by weight, 0 ⁇ Cr ⁇ 4% by weight, remainder Fe.
  • the base substrate is used in one embodiment in an acidic atmosphere at temperatures up to about 250 ° C. This atmosphere arises, for example, in exhaust gases.
  • the substrate may be a part of an exhaust system of a vehicle or a part of a heating system or a heat system or a flue gas system.
  • the invention also provides the use of a Cr (VI) -free silane layer as the middle layer of a three-layer Cr (VI) -free corrosion resistant coating, which middle layer is supported on a Cr (VI) -free phosphated steel substrate or on a phosphated Fe part -based alloy is arranged.
  • the invention also provides the use of a Cr (VI) -free nanoparticle-containing organically modified polysiloxane layer as the topmost layer of a Cr (VI) -free, corrosion-resistant, three-layer coating that is supported on a phosphated steel substrate or on an Fe-based alloy substrate is applied.
  • a method for producing a corrosion-resistant substrate comprises the following steps.
  • a base substrate consisting essentially of a phosphatizable steel or a phosphatable Fe-based alloy is provided.
  • a phosphating layer is applied directly to the surface of the base substrate.
  • a silane layer is applied directly to the phosphating layer by a wet-chemical method, and then an organically modified polysiloxane layer is applied directly to the passivation layer.
  • a base substrate which consists essentially of a phosphated steel or a phosphated Fe-based alloy.
  • the base substrate is therefore already provided with a phosphating layer and a Cr (VI) -free, corrosion-resistant, two-layer coating is applied to this already phosphated substrate.
  • a silane layer is applied directly to the phosphating layer by a wet-chemical method, and then an organically modified polysiloxane layer is applied directly to the passivation layer.
  • the three layers of the corrosion resistant trilayer coating are applied to the base substrate in separate process steps.
  • the three layers can thus be applied by means of different deposition methods based on different principles.
  • the three layers may have different compositions.
  • the phosphating layer can be applied by spraying or dipping. After it has been deposited, the phosphating layer can be dried and optionally cleaned.
  • the organically modified polysiloxane layer comprises epoxy-substituted polysiloxanes and blocked isocyanates. During curing, the epoxy-substituted polysiloxanes are crosslinked via the inherently blocked isocyanates to form a polymer network. The top third layer is thereby formed.
  • Nanoparticles can be formed from a solution to form a compound that has nanoparticles in a polymer network.
  • This sol-gel compound can be applied to the underlying silane layer to form the nanoscale polysiloxane layer.
  • nanoparticles can first form on the silane layer when applied.
  • the solution to be applied can thus be free of nanoparticles.
  • a substrate As a substrate, a part of an exhaust system of a vehicle, a flue gas pipe or a part that is used in an acidic atmosphere at temperatures of up to 250 0 C, can be provided.
  • the substrate may be part of a heating system or a thermal plant.
  • the silane layer can be applied by means of dipping or spraying.
  • the polysiloxane layer can by means of dipping,
  • Syringes or powders are applied. These deposition methods have the advantage that complicated shapes can be completely and reliably coated in less time.
  • the base substrate is thoroughly cleaned prior to application of the phosphating layer.
  • the cleaning measures are selected according to the composition of the substrate and the layer to be applied.
  • the base substrate can be cleaned by aqueous alkaline cleaners. This may be the adhesion of the first passivation layer on the base substrate as well as the coverage improve the first passivation layer.
  • the base substrate may then be further cleaned by acid pickling or by acidic activation of the surface.
  • At least the surface of the silane layer can be dried after the deposition of the silane layer. This improves the adhesion of the upper third polysiloxane layer to the second silane layer and also provides a more reliable coating since water and / or organic constituents of the lower layer are not evaporated after the application of the polysiloxane layer. The formation of bubbles and holes in the coating is thus avoided.
  • the polysiloxane layer can be cured in a further process step.
  • FIG. 1 shows a schematic view of a corrosion-resistant substrate with a three-layer coating
  • FIG. 2 shows mass spectra of a first comparison substrate made of steel with a polysiloxane layer
  • FIG. 3 shows a mass spectrum of the boundary region between the steel and the polysiloxane layer of the first comparative substrate
  • FIG. 4 shows mass spectra of a second comparative substrate with a phosphating layer and a polysiloxane layer applied thereto.
  • FIG. 5 shows mass spectra of the phosphating layer and the polysiloxane layer of the second comparative substrate
  • FIGS. 6 to 8 show mass spectra of a substrate according to the invention with a three-layer coating.
  • FIG. 6 shows mass spectra of the boundary between the
  • FIG. 7 shows a mass spectrum of the transition phase between the phosphating layer and the silane layer applied thereon
  • FIG. 8 shows mass spectra of the third top polysiloxane layer and the interface between this polysiloxane layer and the underlying silane layer.
  • FIG. 1 shows a schematic view of a substrate 10 made of a phosphatizable steel base substrate 1, which has a dreilagige coating 2, 4, 5 according to the invention.
  • a phosphating layer 2 is disposed directly on the surface 3 of the steel base substrate 1.
  • a second layer 4 comprising silane is directly on the phosphating layer 2 and a third layer 5, which has organically modified polysiloxane, and which is arranged directly on the second silane layer 4.
  • the second silane layer is applied to the phosphating layer 2 by means of a wet-chemical method.
  • a sol-gel method is used to prepare the organically modified polysiloxane layer.
  • a part 1 made of a phosphatable steel is first provided, which serves as a base substrate 1 for the coating, and cleaned by commercially available aqueous alkaline cleaners.
  • the base substrate 1 is coated with a zinc phosphating layer 2.
  • Zinc-calcium phosphating, zinc-manganese phosphating, manganese phosphating or chlorate-promoted zinc phosphating may also be used.
  • a commercially available phosphating solution can be used. The solution is applied to the substrate by means of dipping and then the first phosphating layer of the three-layer coating is dried.
  • the second silane layer 4 of the corrosion-resistant three-layer coating has aminopropyltriethoxysilane and was applied to the phosphated surface 6 of the base substrate 1 by dipping with a commercially available product Gardolene 6890 from Chemimet GmbH, Frankfurt, Germany. Thereafter, the coated part 1 was dried.
  • the third polysiloxane layer 5 was applied to the second silane layer 4 by a spraying method.
  • a third solution was provided for Position of the Polysiloxa ⁇ Mrs 5, a third solution was provided.
  • This third solution is a curable composition comprising at least one hydrolysis product of an organosilane having an epoxy group as a functional group and at least one blocked polyisocyanate. Such solutions are described in DE 10 52 853.
  • Suitable solutions on this basis are commercially available from NTC Nano Tech Coatings GmbH.
  • the products Clearcoat U-SiI 120 BW and Clearcoat Ü-Sil 110 from NTC Nano Tech Coatings GmbH, Tholey, Germany were used to produce the third upper polysiloxane layer.
  • the third polysiloxane layer 5 is applied by spraying and then cured.
  • the information provided by the manufacturer was used to deposit the third polysiloxane layer 5 and cure the applied layer.
  • the epoxy-substituted polysiloxane Upon curing, the epoxy-substituted polysiloxane is crosslinked via the inherently blocked isocyanates.
  • the third layer 5 forms via nanoparticles to a dense polymer network.
  • the total thickness d of the three-layer coating 2, 4, 5 is in the range l ⁇ m ⁇ d ⁇ 30 microns. Increased corrosion protection is already achieved with layer thicknesses from 1 ⁇ m to 2 ⁇ m. A total thickness of 2 microns ⁇ d ⁇ 25 microns has also proved to be suitable.
  • Parts 1 made of steel or a phosphatizable iron-based alloy, which are already coated with a phosphating layer can be used as a substrate.
  • a method according to the invention only the second silane layer and the third polysiloxane layer, as described above, are applied to the substrate. This method is used on substrates that are already commercially available with a phosphating layer. The corrosion resistance of commercially available finished parts can thus be improved.
  • the corrosion resistance of the coated substrates according to the invention is investigated in highly corrosive atmospheres.
  • Zinc-phosphated steel substrates with a wet-chemically applied silane layer and a third nanoscale polysiloxane layer applied thereto were provided according to the invention.
  • the corrosion resistance of these substrates in highly corrosive atmospheres was investigated by condensed water climate tests (DIN ISO 3231) in a sulfur dioxide atmosphere. 30 cycles were performed.
  • the layer structure, including the composition, and the layer thickness of the substrates according to the invention were investigated by means of laser desorption mass spectroscopy, LAMMA, and secondary neutral particle spectroscopy, SNMS.
  • Inventive substrates having a three-layer coating of a first phosphating layer, a second silane layer and a third isocyanate-crosslinked polysiloxane layer were investigated.
  • the third layer is referred to as sol-gel layer or SG, since the third isocyanate-crosslinked polysiloxane layer was applied by means of a sol-gel process.
  • a first comparative substrate having a single isocyanate crosslinked polysiloxane layer and a second comparative substrate having a phosphating layer and a polysiloxane layer coated thereon were prepared and tested by means of the above-mentioned materials and methods.
  • the second silane layer is produced with the product Gardoline 6890 and the third polysiloxane layer with the product Clearcoat U-SiI 120 BW by means of a sol-gel process.
  • each sample was irradiated with laser in several places.
  • the mass spectra were recorded at various locations from the surface down to the depth of the steel base material.
  • the analyzed sample area per Laser pulse was about 1 to 20 microns 2 .
  • the residual gas pressure in the sample chamber was 0.5 nbar. The analysis was carried out in such a way that a depth profile was generated at each point.
  • the approximately constant removal rate per laser pulse was about 80 to 120 nanometers.
  • the coating structure is irradiated on the surface with an Nd: YAG laser and the coating is mass spectroscopically analyzed over a depth profile from the upper sol-gel layer (organically modified polysiloxane) via the silane layer and phosphating layer to the steel substrate.
  • FIG. 2 shows LAMMA mass spectra of the first comparison substrate.
  • the spectrum of the steel substrate (steel St 37/2) is shown in FIG. 2 a and the spectrum of the polysiloxane layer in FIG. 2 b.
  • the LAMMA investigations assume a layer thickness in the vicinity of 5 ⁇ m.
  • the boundary between the polysiloxane layer and the base material of the substrate is sharp compared to the following substrates.
  • a spectrum of this boundary region can be seen in FIG.
  • the second comparative substrate has a two-layer coating.
  • a first zinc-calcium phosphate layer is applied to the steel and a second polysiloxane layer, as in the first comparative substrate, to this lower phosphating layer.
  • LAMMA investigations of this second comparative substrate are shown in FIGS. 4 and 5.
  • FIG. 4 shows a mass spectrum of the base material in FIG. 4a and a mass spectrum of the transition region between the base material and the phosphating layer in FIG. 4b of the second comparison substrate.
  • FIG. 4b shows the spectrum of the transition region between the base material and the phosphating or conversion layer.
  • the phosphating layer has zinc-calcium-phosphate compounds.
  • FIGS. 5a and 5b The mass spectrum of the phosphating layer and the polysiloxane sol-gel layer of this second comparative substrate are shown in FIGS. 5a and 5b. About the depth profile of
  • FIGS. 4 and 5 show that the transition phase between the steel base material and the zinc-calcium phosphate layer is substantially wider than the transition phase between the phosphate layer and the sol-gel layer.
  • FIGS. 6 to 9 show the mass fragments of a substrate according to the invention having a three-layer coating analyzed by LAMMA spectroscopy.
  • phosphating layer 2 ⁇ m to 4 ⁇ m silane layer 0.5 ⁇ m
  • polysiloxane layer 5 ⁇ m to 10 ⁇ m Based on an erosion rate of 200 to 250 nm / laser pulse, the following layer thicknesses were calculated: phosphating layer 2 ⁇ m to 4 ⁇ m, silane layer 0.5 ⁇ m and polysiloxane layer 5 ⁇ m to 10 ⁇ m.
  • FIG. 6 shows the conversion behavior of the zinc-calcium phosphating at the boundary layer to the base material. No sharp delamination is shown as in the second comparative substrate.
  • FIG. 7 shows the LAMMA spectrum of the transition phase between the first phosphating layer and the second silane layer. In this area, mass fragments of the two layers are assigned.
  • FIG. 8a shows a mass spectrum of the polysiloxane top layer.
  • FIG. 8b shows a mass spectrum of the boundary region between the silane layer and the polysiloxane layer.

Abstract

Un substrat anticorrosion (10) est recouvert d'un revêtement anticorrosion à trois couches (2, 4, 5) exempt de Cr(VI). Le substrat (10) est essentiellement constitué par un acier pouvant être phosphaté ou par un alliage à base de Fe pouvant être phosphaté. L'invention est caractérisée en ce qu'une couche de phosphatation (2) est directement appliquée sur un substrat de base (1), une couche de silane (4) est directement appliquée sur la couche de phosphatation (2), et une couche de polysiloxane modifiée organiquement (5) est directement appliquée sur la couche de silane (4).
PCT/DE2007/000913 2006-07-06 2007-05-21 Substrat anticorrosion et son procédé de production WO2008003273A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP07764332A EP2041333A2 (fr) 2006-07-06 2007-05-21 Substrat anticorrosion et son procédé de production

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200610031492 DE102006031492A1 (de) 2006-07-06 2006-07-06 Korrosionsbeständiges Substrat und Verfahren zu dessen Herstellung
DE102006031492.1 2006-07-06

Publications (2)

Publication Number Publication Date
WO2008003273A2 true WO2008003273A2 (fr) 2008-01-10
WO2008003273A3 WO2008003273A3 (fr) 2008-04-03

Family

ID=38664145

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE2007/000913 WO2008003273A2 (fr) 2006-07-06 2007-05-21 Substrat anticorrosion et son procédé de production

Country Status (3)

Country Link
EP (1) EP2041333A2 (fr)
DE (3) DE202006020021U1 (fr)
WO (1) WO2008003273A2 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010030115A1 (de) 2009-08-11 2011-02-17 Evonik Degussa Gmbh Glycidyloxyalkylalkoxysilan-basierte wässrige Silansysteme für den Blankkorrosionsschutz und Korrosionsschutz von Metallen
EP3137564B1 (fr) 2014-04-25 2019-12-18 Teknologisk Institut Composition de revêtement, procédé de fabrication du revêtement et son utilisation
WO2020163586A1 (fr) * 2019-02-08 2020-08-13 Minimax Viking Research & Development Gmbh Extincteur automatique de protection contre l'incendie ayant des éléments en matériau à gradient & procédés d'évaluation de l'utilisation dans un environnement corrosif

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102017207594A1 (de) * 2017-05-05 2018-11-08 Federal-Mogul Nürnberg GmbH Thermische Isolierung eines Stahlkolbens mittels einer Mangan-Phosphat- und einer Polysilazan-Schicht

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1052853B (de) 1957-12-19 1959-03-12 Friedr Dick G M B H Wetzstahl
US6375726B1 (en) 2000-10-31 2002-04-23 The United States Of America As Represented By The Secretary Of The Navy Corrosion resistant coatings for aluminum and aluminum alloys
DE10152853A1 (de) 2001-10-25 2003-05-15 Ntc Nano Tech Coatings Gmbh Mischung und Verfahren zur Herstellung von vernetzten Massen auf der Grundlage von modifizierten Polysiloxanen sowie damit hergestellte Überzüge und Formkörper

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5326594A (en) * 1992-12-02 1994-07-05 Armco Inc. Metal pretreated with an inorganic/organic composite coating with enhanced paint adhesion
US5531820A (en) * 1993-08-13 1996-07-02 Brent America, Inc. Composition and method for treatment of phosphated metal surfaces
US5433976A (en) * 1994-03-07 1995-07-18 Armco, Inc. Metal pretreated with an aqueous solution containing a dissolved inorganic silicate or aluminate, an organofuctional silane and a non-functional silane for enhanced corrosion resistance
DE19814605A1 (de) * 1998-04-01 1999-10-07 Kunz Gmbh Mittel zur Versiegelung von metallischen, insbesondere aus Zink oder Zinklegierungen bestehenden Untergründen
DE19956383A1 (de) * 1999-11-24 2001-05-31 Henkel Kgaa Verfahren zur Phospatierung mit metallhaltiger Nachspülung
CA2426081C (fr) * 2000-10-11 2012-02-07 Chemetall Gmbh Procede de pretraitement et / ou d'enduction de surfaces metalliques avant le formage a l'aide d'une couche de type peinture et utilisation des substrats ainsi recouverts
US20060099332A1 (en) * 2004-11-10 2006-05-11 Mats Eriksson Process for producing a repair coating on a coated metallic surface
DE102005015576C5 (de) * 2005-04-04 2018-09-13 Chemetall Gmbh Verfahren zur Beschichtung von metallischen Oberflächen mit einer wässerigen Zusammensetzung und Verwendung der nach den Verfahren beschichteten Substrate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1052853B (de) 1957-12-19 1959-03-12 Friedr Dick G M B H Wetzstahl
US6375726B1 (en) 2000-10-31 2002-04-23 The United States Of America As Represented By The Secretary Of The Navy Corrosion resistant coatings for aluminum and aluminum alloys
DE10152853A1 (de) 2001-10-25 2003-05-15 Ntc Nano Tech Coatings Gmbh Mischung und Verfahren zur Herstellung von vernetzten Massen auf der Grundlage von modifizierten Polysiloxanen sowie damit hergestellte Überzüge und Formkörper

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010030115A1 (de) 2009-08-11 2011-02-17 Evonik Degussa Gmbh Glycidyloxyalkylalkoxysilan-basierte wässrige Silansysteme für den Blankkorrosionsschutz und Korrosionsschutz von Metallen
WO2011018285A1 (fr) 2009-08-11 2011-02-17 Evonik Degussa Gmbh Systèmes de silane aqueux pour la protection contre une corrosion blanche et la protection contre une corrosion de métaux
DE102010030111A1 (de) 2009-08-11 2011-02-17 Evonik Degussa Gmbh Wässrige Silansysteme für den Blankkorrosionsschutz und Korrosionsschutz von Metallen
DE102010030114A1 (de) 2009-08-11 2011-02-17 Evonik Degussa Gmbh Wässriges Silansystem für den Blankkorrosionsschutz und Korrosionsschutz
DE102010030114B4 (de) 2009-08-11 2021-11-04 Evonik Operations Gmbh Wässriges Silansystem für den Blankkorrosionsschutz, Verfahren zu dessen Herstellung, dessen Verwendung sowie mit diesem behandelte Gegenstände und Korrosionsschutzschicht
EP3137564B1 (fr) 2014-04-25 2019-12-18 Teknologisk Institut Composition de revêtement, procédé de fabrication du revêtement et son utilisation
WO2020163586A1 (fr) * 2019-02-08 2020-08-13 Minimax Viking Research & Development Gmbh Extincteur automatique de protection contre l'incendie ayant des éléments en matériau à gradient & procédés d'évaluation de l'utilisation dans un environnement corrosif

Also Published As

Publication number Publication date
DE102006031492A1 (de) 2008-01-10
EP2041333A2 (fr) 2009-04-01
DE202006020021U1 (de) 2007-11-29
WO2008003273A3 (fr) 2008-04-03
DE202007007303U1 (de) 2007-11-08

Similar Documents

Publication Publication Date Title
EP1987172A2 (fr) Substrat anticorrosif et son procede de fabrication
DE69909054T2 (de) Oberflächenbehandeltes stahlblech für brennstofftanks und verfahren zu dessen herstellung
DE3640662C2 (fr)
EP1960483A2 (fr) Materiau de revetement destine a la protection de metaux, notamment d'acier, contre la corrosion et/ou l'oxydation, procede de revetement de metaux et element metallique
DE2325138C3 (de) Verfahren zur Bildung von Schutzüberzügen auf Metallsubstraten
EP2145031A2 (fr) Prétraitement de métallisation de surfaces de zinc
WO2001030923A2 (fr) Revetements organiques conducteurs
DE3838452A1 (de) Mit einer zinklegierung plattiertes korrosionshinderndes stahlblech mit einem organischen ueberzug und verfahren zu seiner herstellung
WO2008080746A2 (fr) Revêtements organiques conducteurs à faible épaisseur de couche et bonne aptitude au formage
DE3417844C2 (de) Mit Eisen-Zinklegierung elektrogalvanisiertes Stahlblech mit einer Mehrzahl von Eisen-Zinklegierung-Beschichtungen
DE102006062500A1 (de) Mittel und Verfahren zum Beschichten von Metalloberflächen
DE10297178B4 (de) Korrosionsbeständige Beschichtungsfilmstruktur, die kein kein sechswertiges Chrom enthält
WO2008003273A2 (fr) Substrat anticorrosion et son procédé de production
WO2011113575A1 (fr) Procédé de fabrication d'une bande métallique revêtue
WO2003029508A1 (fr) Composants metalliques dotes d'un revetement protecteur
EP2743376B1 (fr) Agent aqueux et procédé de revêtement pour le traitement anti-corrosion de substrats métalliques
DE3835475C2 (de) Stahlblech für Automobilkarosserien und Verfahren zu dessen Herstellung
WO2021139973A1 (fr) Élément métallique renfermant du fer pourvu d'une couche de brunissage alliée
DE202007002788U1 (de) Korrosionsbeständiges Substrat
DE10014035B4 (de) Gefärbte Konversionsschicht, eine Lösung zu ihrer Herstellung sowie ihre Verwendung
DE10055215A1 (de) Passivierungsverfahren
DE102016114808A1 (de) Verfahren zum Schutz eines Gehäuses eines Steckverbinders vor Korrosion
DE4333894C1 (de) Verfahren zur Harzvergütung einer Metalloberfläche
DE102021121343A1 (de) Stahlflachprodukt mit verbesserter Zinkbeschichtung
EP3325844B1 (fr) Élément de chaîne et son procédé de fabrication

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 2007764332

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: RU

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07764332

Country of ref document: EP

Kind code of ref document: A2